Esta pesquisa estudou o método de realcalinização química (RAQ), através da absorção e difusão de soluções alcalinas na superfície do concreto carbonatado. Neste estudo foram utilizadas três espécies químicas para obtenção das soluções alcalinas: carbonato de sódio, hidróxido de potássio, e hidróxido de cálcio. Para avaliar a eficácia desta nova técnica de reabilitação, foram realizadas medidas de profundidade de carbonatação e de realcalinização, medidas eletroquímicas de potencial de corrosão e de espectroscopia de impedância eletroquímica (EIE) para a verificação do estado da armadura, ensaios de imersão, absorção e ascensão capilar em concretos de referência, carbonatados e realcalinizados. Em razão da falta de conhecimento sobre a eficácia da técnica de realcalinização eletroquímica (RAE) em relação à repassivação da armadura, em paralelo foi realizado o estudo da repassivação das armaduras na RAE. Em relação à durabilidade da técnica, foi avaliada a resistência do concreto recuperado quando submetido a um novo ciclo de carbonatação acelerada, analisando as novas profundidades de carbonatação para cada solução alcalina estudada. Na repassivação da armadura com a técnica de RAE, a solução de carbonato de sódio proporcionou valores de potencial de corrosão mais eletropositivos do que a solução de KOH, e gráficos de EIE similares aos obtidos com a solução de KOH. Na RAQ, a solução de KOH foi mais eficiente, sendo os resultados de potencial de corrosão similares aos obtidos com a solução de carbonato de sódio, no entanto, com valores de impedância e ângulo de fase superiores aos obtidos com carbonato de sódio. A solução de hidróxido de cálcio foi a que obteve os melhores valores de potencial de corrosão, proporcionando às barras valores mais eletropositivos do que antes da carbonatação. No entanto, a RAQ utilizando a solução de hidróxido de cálcio não propiciou a realcalinização do cobrimento do concreto, devendo então ser melhor estudada e, até que sua eficácia seja melhor entendida, sua aplicação deve ser vista com ressalvas. Ao final dos experimentos foi possível verificar que a RAQ aumentou bastante a durabilidade do cobrimento do concreto quando submetido a um novo ciclo de carbonatação acelerada. Enquanto os corpos-de-prova de referência ao final dos 45 dias de ensaio de carbonatação acelerada foram quase que totalmente carbonatados, os corpos-de-prova realcalinizados com as soluções de carbonato de sódio e hidróxido de potássio não apresentavam qualquer indício de carbonatação. / This research studied the method of chemical realkalisation (CRA), through the absorption and diffusion of alkalis in the carbonated concrete surface, as a new technique of rehabilitation. The experimental program was conducted in three set of concrete specimens: reference, carbonated and CRA treated. The CRA method was studied with three types of alkaline solutions: sodium carbonate, potassium hydroxide and calcium hydroxide. To evaluate the effectiveness of CRA treatment was carried out measures of depths of carbonation and realkalisation; electrochemical measurements of potential and electrochemical impedance spectroscopy (EIS) to verify the condition of steel bars; immersion, absorption and capillary tests. Besides these tests, the study of repassivation in corroded steel bars when applied the technique of electrochemical realkalisation (ERA) was also performed in parallel, since their effectiveness is considered unclear in various studies regarding the durability of the technique. The concrete treated with CRA method was submitted to a new accelerated carbonation cycle, and new measurements of carbonation depth were made for each alkaline solution applied. The repassivates reinforcements with ERA technique showed that the sodium carbonate solution provided corrosion potential values more electropositive than the KOH solution, and EIS graphics are similar those obtained with the KOH solution. In CRA technique, the KOH solution was more efficient, and the results of corrosion potential are similar those obtained with the sodium carbonate solution, however, with the results of impedance and phase angle higher than for sodium carbonate solution. The calcium hydroxide solution showed the best results of corrosion potential, providing bars more electropositive than before carbonation. However, the calcium hydroxide solution not provided the concrete realkalisation, and this alkaline solution should be more studied. Their implementation must be viewed with exceptions until its effectiveness has been proved. At the end of durability experiments was possible to verify that the CRA greatly increased the concrete durability when subjected to a new accelerated carbonation cycle. After 45 days of testing, the reference concrete specimens were almost totally carbonated. Therefore, the concrete specimens realkalised with sodium carbonate and potassium hydroxide solutions were no carbonation indication.

Este trabalho apresenta uma análise do comportamento da frente de carbonatação em vigas de concreto armado sob tensão, em escala natural e reduzida, com a máxima condição de subarmação. As vigas foram construídas com e sem adição da sílica da casca de arroz e sílica de ferro silício ou silício metálico. Para cada viga em escala natural (agregado graúdo com D máx. = 19 mm) foi moldada uma em escala reduzida com o mesmo traço de concreto para estabelecer os mesmos parâmetros de comparação. As vigas foram curadas durante 7 dias e posteriormente submetidas à flexão, com o carregamento aplicado nos terços (L/3 da viga). Realizou-se o pré-condicionamento para a estabilização da umidade interna das vigas que foram expostas durante 28 dias em um ambiente com concentração de 50% de dióxido de carbono, umidade relativa de 65 \'+ OU -\' 5% e temperatura ambiente. Foram determinados: resistências à compressão simples axial, resistência à tração por compressão diametral, módulos de elasticidade e profundidade da frente de carbonatação em corpos-de-prova cilíndricos. A profundidade da frente de carbonatação em corpos-de-prova foi determinada para diferentes concentrações de dióxido de carbono. Também foi verificada a carbonatação ao longo das vigas em escala natural e reduzida e nas posições das fissuras. Para a previsão da profundidade da frente de carbonatação nas vigas, foram ajustadas equações para a representação da carbonatação na região das fissuras. Os resultados obtidos mostraram a eficiência da espessura do cobrimento, a eficácia dos modelos físicos reduzidos para realizar estudos de carbonatação e a tendência da carbonatação em elementos estruturais na condição de serviço. A frente de carbonatação difere na posição das fissuras, evidenciando um comportamento diferente quando comparado com corpos-de-prova. A análise microestrutural ilustrou o comportamento da frente de carbonatação em vigas de concreto armado, complementando o estudo experimental. Com base nos resultados obtidos pode-se afirmar que a simples adoção de concretos de alto desempenho para construção de elementos estruturais não é suficiente nas peças que contenham fissuras e que sejam submetidas a atmosferas ambientais agressivas. / This work reports on the behavior of carbonation in reinforced concrete beams under stress regime on full and small scales having the lowest possible frame. The beams were made with and without adding silica from rice husk and silica fume (Fe-Si). For each beam on a full scale (coarse aggregate with D máx. = 19 mm) another beam on a small scale was made with the same mix of concrete to maintain the same comparison parameter. The beams were cured for 7 days and subsequently submitted to flexure by applying a two-point loading (L/3 of beam). Humidity stabilization to stabilize internal humidity of beams exposed for 28 days in an environment with a concentration of 50% carbon dioxide, 65 \'+ OR -\' 5% of relative humidity and room temperature was carried out. The following was determined: axial compression strength, tensile splitting strength, young\'s modulus and carbonation depth in cylindrical specimens. The carbonation depth was determined in specimens with unlike carbon dioxide concentration. Moreover, carbonation along beams on full and small scales and in cracks was observed. To estimate the carbonation depth of the beams, equations were adjusted to represent the carbonation in cracks. The results show the efficiency in the thickness of the cover, efficiency of small-scale models for studies concerning carbonation and behavior of carbonation in the serviceability of structural elements. The carbonation depth differs in the position of cracks, showing behavior which is unlike the one compared to specimens. The microstructure analyses show the behavior of carbonation depth in reinforced concrete beams complementing the experimental study. The results show that it is not sufficient to use high performance concretes in structural elements for elements with cracks and in aggressive atmospheres.

Embora a utilização do concreto de alto desempenho (CAD) para a fabricação de elementos pré-moldados seja frequentemente usado na construção civil, o presente trabalho apresenta um estudo do emprego de microconcreto em aduelas tubulares de pequenas espessuras protendidas dentro de critérios fabris, com materiais regionais, a fim de repassar para a iniciativa privada os resultados colhidos das análises já elaboradas. As aduelas servirão para compor o tabuleiro de passarelas estaiadas, com a intenção de projetar uma estrutura que, além de harmônica aos olhos e arrojada, também seja econômica, pois se aplicando a protensão nas aduelas que formam o tabuleiro, pode-se explorar uma das características que os concretos de alto desempenho e resistência têm de melhor, que é a resistência à compressão (> 80MPa). Os materiais utilizados na dosagem do microconcreto para a confecção dos elementos em escala real, foram os seguintes: CP V ARI RS, sílica de ferro-silício em substituição volumétrica ao cimento em 10%, três tipos de areias de cava da região para o melhor empacotamento das partículas reduzindo os vazios, pedrisco basáltico com dimensão máxima de 9,5 mm em consonância com as características geométricas do elemento estrutural e da armadura e um superplastificante para atingir a consistência desejada. Levaram-se em conta na produção desse trabalho os recentes desenvolvidos havidos na reologia dos concretos frescos, ação da carbonatação e ação de cloretos. A consistência do concreto foi um fator importante para a determinação do traço, pois o concreto foi lançado nos moldes a uma altura de 2,40 m, permanecendo coeso. A concretagem foi realizada através de betonadas consecutivas para o total preenchimento do molde, onde em todas as betonadas foram realizadas a mesma seqüência de mistura pré-estabelecida. Foram moldadas duas aduelas em escala real, as quais foram estudadas seguindo a simulação do processo de montagem e uso da passarela, a fim de se analisar as solicitações atuantes e as formas de ruína das aduelas acopladas. As resistências mecânicas dos corpos-de-prova foram analisadas nas idades de 1, 3, 7, 28, 63 e 91 dias, cujos resultados de resistência à compressão simples, compressão diametral e o módulo de elasticidade atingiram ao previsto no projeto. O acabamento superficial, o tempo de lançamento, adensamento, desforma, cura e o transporte foram adequados para o reaproveitamento dos moldes. Com os resultados obtidos das análises realizadas com os dois módulos do tabuleiro, verificou-se a possibilidade de construir passarelas com elementos tubulares de pequena espessura protendidos com barras de Dywidag pelo sistema de protensão proposto. Verificou-se também uma pequena amplitude das deformações e deslocamentos das aduelas no processo de montagem e uso da passarela, assim como no transporte das aduelas. Não foram observadas a formação de quaisquer tipos de fissuras durante todo o processo envolvido, quais sejam, desmoldagem, estocagem, transporte, lançamento e utilização simulada. / Although the use of high performance concrete (HPC) for precast elements manufacture is frequently used in civil construction, this work presents a study of the utilization of microconcrete in prestressed small thicknesses tubular barrel stave, in manufacturing criteria, with regional materials, in order to repass to private initiative the already elaborated analyses results. Barrel stave will serve to compose cable-stayed footbridge deck, with the intent to project a structure that, beyond pleasant and bold, must be also economic, therefore applying prestress in barrel stave to form the deck, it\'s possible to explored the most important high performance and strength concrete characteristics, the compressive strength (> 80MPa). The used materials to design a microconcrete for the elements confection in real scale, are the following: CP V ARI RS, ferrosilicon silica fume in 10% volumetric substitution to the cement, three types of regional sands for optimum particles packing to reduce the emptinesses, 9,5 mm basaltic grave in accord with the geometric characteristics of the structural element and reinforcement, and superplasticizer additives to reach the desired consistency. Recent researches about fresh concrete rheology, carbonation and chloride action had been taken in account in the production of this work. The consistency was an important factor for concrete design, therefore the concrete would be was launched in 2,40 m height molds, remaining united. The molding was carried through consecutive load concrete mixer operation for the total fulfilling of the mold, where in all load of a concrete mixer had been carried through the same sequence of pre-established mixture. Two were molded barrel stave full scale, which were studied in the simulation of process of assembly and use of footbridge in order to examine the requests engaged in the forms of ruin from barrel stave coupled. The mechanical strength of the samples had been analyzed in ages of 1, 3, 7, 28, 63 and 91 days, whose results of simple compressive strength, diametrical compression and the modulus of elasticity had reached to the foreseen in project. The superficial finishing, the time of launching, compacting, desmoulding, cure and the transport had been adjusted for molds reuse. With the results of analyses conducted with two modules of deck, there was the possibility of building footbridges with tubular elements of small thickness prestressed with bars of Dywidag the system protention proposed. There was also a small extent of deformation and displacement of barrel stave in process of assembly and use of footbridge as well as the transport of barrel stave. Not been observed the formation of any types of cracks during all the involved process, which are, desmoulding, storage, transport, launching and simulated use.

O presente estudo teve como objetivo produzir e avaliar o desempenho de painéis de partículas homogêneas de cimento-bagaço de cana-de-açúcar curados por carbonatação acelerada. Para atingir os resultados foram realizados ensaios de caracterizações morfológica e físico-química das partículas de bagaço de cana-de-açúcar, bem como ensaio de termometria para identificar a compatibilidade da matéria prima (bagaço) com o cimento. Os painéis de partículas cimento-bagaço produzidos foram submetidos a dois processos de cura distintos: 1- cura por 48 h em câmara climática, seguida por 24 h em ambiente com concentração de 15% ±0.6 de CO2, seguida por 24 dias em ambiente saturado ao ar; 2- cura em câmara climática por 48 h, seguida por 25 dias em ambiente saturado ao ar. Ao final dos 28 dias de cura e após ensaio de envelhecimento acelerado de imersão e secagem foram realizadas as caracterizações físico-mecânicas seguindo as recomendações das normativas DIN: 310; 322 e 323, bem como caracterização microestrutural e de condutividade térmica do painel de partículas cimento-bagaço. Os resultados obtidos indicaram que os painéis de partículas cimento-bagaço curados por carbonatação acelerada apresentaram melhor desempenho físico-mecânico quando comparados aos painéis não carbonatados, pois a carbonatação melhorou a interface entre as partículas e a matriz cimentícia, proporcionando maior adesividade entre as fases. E, além disso, reduziu o pH do meio alcalino em que as partículas de bagaço de cana-de-açúcar estão inseridas, minimizando o processo de degradação da lignina, celulose e hemicelulose. / The present study aimed to produce and evaluate the performance of homogeneous particles of cement panels-bagasse-sugar cured by accelerated carbonation. To achieve the results tests were carried out morphological and physical-chemical characterization of particles of bagasse of sugar cane, as well as Thermal-test to identify the compatibility of the raw material (bagasse) with cement. The particle cement-bagasse produced were subjected to two different curing processes: 1-cure for 48 h in climate Chamber, followed by 24 h in environment with concentration of 15% ± 0.6, followed by 24 days in saturated air environment; 2-cure in climate Chamber for 48 h, followed by 25 days in saturated air environment. At the end of the 28 days of curing and after accelerated aging test of soaking and drying were realized the physical-mechanical characterizations according the recommendations of the DIN standards: 310; 322 and 323, as well as micro-structural characterization and thermal conductivity of Particleboard bagasse-cement. The results obtained indicated that the particle bagasse-cement cured by accelerated carbonation presented physical-mechanical performance better than compared with non-carbonated panels because the carbonation has improved the interface between the particles and the cementitious matrix, providing greater adhesion between phases. In addition, reduced the pH of the alkaline medium in which the particles of bagasse of sugar cane are inserted, minimizing the process of degradation of lignin, cellulose and hemicellulose.

Une solution pour réduire l’impact environnemental du béton est de substituer une partie du ciment par des additions minérales, comme le laitier de hauts fourneaux. Néanmoins, cette substitution ne doit pas réduire les performances du matériau vis-à-vis de la carbonatation, l’un des principaux phénomènes de vieillissement des structures en béton armé. La carbonatation est une réaction chimique entre la matrice cimentaire et le dioxyde de carbone présent dans l’air. Cette réaction, en plus de former du carbonate de calcium, diminue le pH de la solution interstitielle rendant ainsi les armatures vulnérables à la corrosion. Les essais accélérés de carbonatation montrent, en laboratoire, une grande disparité de comportements entre matériaux cimentaires très faiblement poreux à hautes performances mécaniques et matériaux plus poreux en usage dans les ouvrages courants. L’objectif de cette thèse est de mieux comprendre le phénomène de carbonatation des matériaux cimentaires, notamment ceux contenant du laitier de hauts-fourneaux. Nous avons procédé en découplant les phénomènes impliqués dans la carbonatation que sont la diffusion gazeuse, les réactions chimiques et les transferts hydriques (séchage). La première partie de ces travaux de thèse a nécessité le développement et la validation d’un dispositif de mesure expérimental du coefficient de diffusion du CO2. Ce dernier a permis une étude paramétrique sur pâtes mettant en évidence l’influence de la composition et de la carbonatation sur la diffusion. La seconde partie a porté sur l’étude des cinétiques de carbonatation de pâtes en fonction du degré de saturation, après une mise à l’équilibre hydrique sur une longue période. Ces cinétiques ont été étudiées, sur échantillons de faibles dimensions, au moyen d’un suivi des évolutions pondérales et d’analyses thermogravimétriques, pour l’identification des hydrates résiduels et des carbonates formés. Nous avons ainsi mis en évidence des différences de comportement des hydrates et des liants vis-à-vis de la carbonatation impliquant la microstructure du matériau. / One solution for reducing the environmental impact of concrete is to substitute a part of cement by mineral additions, such as granulated blast furnace slag. However, this substitution should not reduce the performances of concrete with respect to carbonation, one of the main ageing phenomena of reinforced concrete structures. Carbonation is a chemical reaction between the cement matrix and the carbon dioxide from the atmosphere. In addition to the formation of calcium carbonate, this reaction results in a pH reduction of the pore solution and a risk of corrosion. Laboratory accelerated tests show a wide disparity between the carbonation resistance of high mechanical performances concretes with low porosity and the resistance of more porous and more usual ones. The objective of this thesis is to better understand the phenomenon of carbonation of cementitious materials, including those containing blast furnace slags. This work was carried out by decoupling the phenomena involved in carbonation that are gaseous diffusion, chemical reactions and water transfers. First, an experimental device for measuring the CO2 diffusion coefficient was developed. After validation, the latter was used in a parametric study carried out on cement pastes showing the influence of composition and carbonation on the diffusion coefficient. The second part of the thesis work focused on studying the kinetics of carbonation of pastes with respect to the degree of water saturation. Prior to carbonation, the studied pastes were conserved during a long period at various RH to achieve hydric equilibrium. The carbonation kinetics of small size samples of pastes was studied by means of monitoring of weight changes and thermogravimetric analyzes for identification of residual hydrates and formed carbonates. We have thus shown differences in behavior of hydrates and binders during carbonation involving the material microstructure.

Le futur site de stockage géologique des déchets MAVL français intègre, dans sa conception, des éléments de structure en béton armé (alvéole et conteneurs). Prédire leur durabilité à l'échelle de la phase d'exploitation (environ 100 ans) est décisif. En conditions de service, le système de ventilation assurerait un approvisionnement constant de CO2, soumettant le béton à des phénomènes de séchage et de carbonatation. L'effet de la température (dû à l'exothermie des déchets) et du séchage sur la carbonatation a été évalué par le passé. Les données acquises à ce jour se doivent cependant d'être complétées. Dans ce sens, la prise en compte des transferts hydriques simultanés à la carbonatation est indispensable. D'une part, car la carbonatation est une pathologie courante du béton armé qui mène, à terme, à une corrosion généralisée des armatures. D'autre part, car la durabilité des structures en béton armé est conditionnée par l'évolution de leur état hydrique tout au long de leur période de service. L'évaluation des propriétés de transport d'eau dans les matériaux carbonatés, en milieu insaturé, constitue un enjeu important pour l'Andra chargée de la gestion des déchets radioactifs.Des essais de carbonatation accélérée sont conduits sur quatre pâtes de ciment durci (CEM I, CEM III/A, CEM V/A et un mélange Bas-pH) à une teneur en CO2 de 3%. Les propriétés hydriques des matériaux carbonatés sont évaluées à partir d'une approche simplifiée nécessitant la connaissance de 3 paramètres physiques accessibles par l'expérience : (i) porosité, (ii) isotherme de désorption de la vapeur d'eau et (iii) perméabilité.Les résultats mettent en évidence des modifications minéralogiques et microstructurales majeures engendrées par la carbonatation : décomposition des hydrates et précipitation de carbonate de calcium (CaCO3) selon différents polymorphes. La décalcification forte des C S H et la polymérisation des chaines silicatées, menant à la formation d'un gel de silice enrichi en calcium, sont constatées. La conséquence directe est l'apparition d'un retrait de carbonatation, lui-même à l'origine d'un phénomène de microfissuration. D'autre part, une réduction du volume poreux et de la surface spécifique des matériaux sont observées. Les carbonates formés obturent les pores, réduisant ainsi la porosité totale. Dans ce sens, plus la teneur initiale en portlandite est élevée, plus la quantité de CaCO3 formée est importante et, par conséquent, plus la chute de porosité résultante est marquée. La structure d'un matériau carbonaté n'a alors plus rien à voir avec son état initial. Ces changements se traduisent par une baisse significative de la teneur en eau à l'équilibre et un changement de morphologie des isothermes, en lien direct avec les évolutions microstructurales. Une baisse de la perméabilité est obtenue dans le cas du ciment Portland (CEM I), en raison du large colmatage de la porosité. Par contre, elle augmente dans le cas des ciments avec ajouts (CEM III/A, CEM V/A et Bas-pH), fait directement imputé à l'effet de la microfissuration, qui prédomine devant la chute de porosité. Le cortège minéralogique initial (teneurs en portlandite et C-S-H) joue donc un rôle déterminant vis-à-vis du comportent des matériaux cimentaires face à la carbonatation. La représentativité de la carbonatation accélérée vis-à-vis de la carbonatation naturelle a, par ailleurs, été vérifiée. Le jeu de données récolté au cours de ces travaux peut être étendu et, appliqué avec confiance, en condition de carbonatation réelle / The French design of deep geological repository involves the use of cement-based materials (vault cell and containers). The durability assessment over the operational phase (supply 100 years) is decisive. In operating conditions, a ventilation system would maintain the CO2 partial pressure within the disposal, subjecting concrete to drying and carbonation. The temperature (due to the waste thermal output) and drying effects on carbonation have been studied in the past. The data acquired must however be complemented. In this sense, taking into account the water transfers simultaneously to carbonation is essential. On the one hand, because carbonation is a common pathology of reinforced concrete that leads to rebar corrosion. On the other hand, because the durability of reinforced concrete structures is dependent on their water content evolution all along their service life. The assessment of water transport properties in carbonated materials, under unsaturated conditions, is an important issue for Andra in charge of the management of radioactive waste in France.Accelerated carbonation test are performed on four hardened cement pastes (CEM I, CEM III/A, CEM V/A and a Low-pH mix) at 3% CO2 content. The water transport properties of carbonated materials are evaluated using a simplified approach, requiring the knowledge of 3 physical parameters, accessible through experimental way: (i) porosity, (ii) water vapour desorption isotherm and (iii) permeability.The results highlight mineralogical and microstructural changes induced by carbonation: hydrates decomposition and calcium carbonate precipitation (CaCO3) according to various polymorphs. The high decalcification of C-S-H and the polymerisation of silicates chains, leading to the formation of a calcium-enriched silica gel, are found. This results in carbonation shrinkage, responsible of microcracking. On the other hand, the reduction of porosity and specific surface area are observed. The formed carbonates fill the pores, reducing the total porosity. In this sense, the higher the initial portlandite content, the higher the amount of CaCO3 and, consequently, the more the porosity decrease. The structure of the carbonated materials is totally different from the initial state. These changes result into a significant reduction of the water content at the equilibrium and a modification of the isotherms morphology, directly related to the microstructure evolutions. The permeability is found to decrease in the case of Portland cement (CEM I), due to porosity clogging. By contrast, it was found to increase significantly for blended cements (CEM III/A, CEM V/A and Low-pH mix), this is directly attributed to the microcracking effect which is more significant compared to porosity clogging. The initial mineralogy (portlandite and C-S-H contents) therefore plays a determinant role regarding to the carbonation impact on the cementitious materials behaviour. Furthermore, the representativeness of accelerated carbonation compared to natural one was verified. The data set acquired during this work can be extended and, applied confidently under real carbonation conditions

La corrosion des aciers est l’une des principales causes de dégradation des ouvrages en béton armé, notamment en façade maritime. Cette dégradation est due à la diffusion d’ions chlorures qui peut se produire dans les ouvrages immergés dans l’eau de mer, ceux subissant des cycles de marnage et également ceux soumis aux embruns marins. La corrosion peut être également due au processus de carbonatation du béton, responsable de la baisse du pH et par conséquent de la dépassivation des aciers. Cette thèse propose un modèle physico-chimique pour décrire la penetration des agents agressifs dans la première phase de la corrosion des aciers. Cette phase dite « incubation » correspond à la phase pendant laquelle le transfert des espèces agressives se produit dans le béton. Afin d’identifier clairement les paramètres de transport de ce modèle macroscopique une démarche multi-échelle est mise en oeuvre pour rendre compte de la diffusion dans les bétons. Cette démarche repose sur une description détaillée de la microstructure du béton (constituants et morphologie) par des méthodes de changement d’échelle. Cette approche se veut la plus exhaustive possible avec la prise en compte explicite de l’influence du rapport eau sur liant de la pâte de ciment, des propriétés des granulats et de la zone de transition entre la pâte et les granulats. Après identification de tous les paramètres d’entrée, le modèle physico-chimique macroscopique est utilisé pour évaluer la durée de vie d’un béton soumis au couplage carbonatation -chlorures en milieu insaturé. Suite à une validation du modèle par comparaison à des résultats expérimentaux, plusieurs applications de ce modèle sont présentées. / The corrosion of steels is one of the principal causes of degradation of reinforced concrete structures, especially in front of the sea. This degradation is due to the diffusion of chloride ions that can occur in the structures immersed in the seawater, those undergoing tidal cycles and also those subjected to the sea spray. The corrosion can also be due to the carbonation process of the concrete, which is responsible for decreasing of the pH and consequently the depassivation of the steels. This thesis proposes a physicochemical model to describe the penetration of aggressive agents in the first period of steel corrosion. This so-called « incubation » period corresponds to the period during which the transfer of aggressive species occurs in the concrete. In order to clearly identify the transport parameters of thismacroscopic model, a multi-scale approach is implemented to consider the diffusion in concretes. This approach is based on taking into account the detailed description of the microstructure of the concrete (constituents and morphology) by upscaling methods. This multi-scale approach is intended to be the most comprehensive with the consideration of the influence of the water-to-binder ratio of the cement paste, the properties of the aggregates and the transition zone between the cement paste and the aggregates. After identifying all the input parameters, the macroscopic physico-chemical model is used to evaluate the service life of a concrete subjected to coupling carbonation -chlorides in unsaturated medium. Following a validation of the model compared to experimental results, several applications of this model are presented.

A busca pelo desenvolvimento sustentável impulsiona a pesquisa voltada ao uso de resíduos industriais na construção civil. Os resíduos da indústria de cerâmica vermelha podem ser utilizados como material pozolânico e já existem trabalhos que apontam para essa possibilidade. Porém, existe uma lacuna quanto à avaliação da durabilidade do concreto produzido com esse resíduo. Este trabalho analisa os efeitos da substituição de parte do cimento por resíduos de tijolos moídos (RTM) frente à corrosão da armadura provocada pela carbonatação e pela ação de cloretos. Para isso, foram preparados concretos convencionais (CCV) nos traços (aglomerante: materiais secos) 1:3,18; 1:4,11; e 1:5,58, cada um com 10%, 20% e 30% de RTM. Foram também analisados concretos autoadensáveis (CAA) com traço de 1:3 e 20%, 30% e 40% de substituição de resíduos, além dos traços sem resíduos usados como referências. O uso do RTM diminuiu o índice de vazios nos traços, porém houve perdas de resistência que alcançaram até 19% aos 90 dias. Os concretos autoadensáveis (CAA) mostraram melhores resultados de resistência apresentando melhoria em todos os traços para a mesma idade dos CCV, atingindo 11% de aumento. Em relação aos ensaios de carbonatação, os concretos com RTM tiveram maiores profundidades de carbonatação do que os concretos de referência, fato explicado pela redução da sua reserva alcalina. No entanto, esse aumento não inviabiliza o uso de concretos com RTM, principalmente para dosagens de menor porosidade e adições em patamares de substituição menos elevados Para a penetração de cloretos o RTM apresentou bom resultado, tanto para os CCV como para os CAA. Embora o RTM tenha diminuído o teor crítico de cloretos, ele aumentou o tempo necessário à despassivação das armaduras. Fato explicado pelo refinamento dos poros e pela maior capacidade de fixação de cloretos. Esse resultado é bastante animador para o uso deste resíduo em concretos convencionais expostos a ambientes marinhos ou como finos para concretos autoadensáveis. / The search for the sustainable development boosts the research focused on the use of industrial wastes civil construction. The industry wastes of red ceramics can be used as pozzolanic material and there are already works that point out for this possibility. However, there is a knowledge gap regarding the durability evaluation of the concrete produced with this waste. This research analyzes the effects substitution of part of the cement by crushed brick wastes (CBW) in relation to the reinforcement corrosion caused by carbonation and chloride action. For this reason, conventional cement concrete (CCV) was prepared in the traces (agglomerate: dry materials) 1:3,18; 1:4,11; and 1:5,58, each one with 10%, 20% and 30% of CBW. Self-compacting concrete (SCC) was also analyzed with trace of 1:3 and 20%, 30% and 40% of waste substitution, besides the traces with no waste used as references. The use of CBW decreased the rate of gaps in the traces, but there were losses of resistance that reached up to 19% in 90 days. The self-compacting concrete (SCC) showed better resistance results presenting improvement in all traces for the same age of the CCV, reaching 11% of increase. In regard to the carbonation tests, the CBW concretes had greater depths of carbonation than the reference concrete; fact explained by the reduction of its alkaline reserve. Nevertheless, this increase does not hamper the use of CBW concretes, especially for dosages of lower porosity and additions in lower substitution standards. For the chloride penetration, the CBW presented good result both for the CCV and the SCC. Although the CBW has diminished its critical chloride content, it increased the necessary period of time for reinforcement despassivation This fact was explained by the refining of pores and by the larger capacity of chlorides fixation. This result is very satisfactory for the use of this waste in conventional concretes exposed to marine environments or as fine aggregate for self-compacting concretes.

L'altération hydrothermale du manteau lithosphérique dans les dorsales médio-océaniques fournit un mécanisme de transfert de chaleur et de masse entre la terre profonde et l'océan recouvrant. Le manteau lithosphérique est constituée de roches ultramafiques, également appelées péridotites. Ils comprennent plus de 70% d'olivine, de pyroxènes associés et de phases minérales mineures. La percolation de l'eau de mer dans le socle ultramafique produit l'altération de l'olivine et des pyroxènes en serpentine par le processus de serpentinisation et il est associé à des réactions d'oxydation et de carbonatation (lorsque le CO2 est présent dans le fluide). Le processus de serpentinisation présente un intérêt particulier pour la production de H2, le stockage du CO2, le développement de la vie et la production de gisements de minerai économiquement intéressants concentrés dans les fumeroles hydrothermaux. La durabilité et l'efficacité des réactions nécessitent la pénétration et le renouvellement des fluides à l'interface fluide-minéral. Les failles et les fractures des détachements océaniques sont les zones hautement perméables qui permettent à l'eau de mer de pénétrer profondément dans le manteau lithosphérique. Cependant, le processus de serpentinisation conduit à la précipitation de minéraux de faible densité qui peuvent remplir le réseau poreux, colmatant les chemins d'écoulement qui peuvent modifier les propriétés hydrodynamiques et la réactivité des roches réagi.Ces travaux de thèse visent à améliorer la compréhension des effets en retour des réactions sur les propriétés hydrodynamique du milieu dans les zones hautement perméables au cours des premières étapes de l'altération du socle ultramafique. Il se concentre en particulier sur les changements de texture et les réactions chimiques des roches ultramafiques en évaluant les effets du (i) débit et (ii) des fluides salins riches en CO2. Deux séries d'expériences de percolation réactive ont été réalisées à T = 170-190°C et P = 25MPa. La première série d'expériences consistait à injecter de l'eau de mer dans des échantillonnes de poudre d'olivine compressé sur une large gamme de débits constants. La tomographie par rayons X de haute résolution a été acquise avant et après l'expérience avec des débits élevés; afin d'évaluer les changements dans la microstructure de la roche lors de la réaction de serpentinisation. La deuxième série d'expériences consistait à injecter des fluides salins riches en CO2 dans des échantillonnes de péridotite fracturés mécaniquement.Les résultats ont permis de différencier: (1) un contrôle du débit du flux à l'échelle du pore peut contrôler la composition du fluide local et le développement de différents chemins de réaction à l'échelle de l'échantillon. (2) Le développement de différentes chemins réactifs et les changements de texture dans la roche dépend de la concentration de CO2 dissous dans la solution. (3) La formation de minéraux carbonatés (MgCO3) peut stocker du CO2 sous forme stable de minéral à long terme. (4) Un contrôle de la concentration de CO2 dissous dans le fluide et du réseau de fractures peut améliorer / limiter l'efficacité du stockage de CO2 dans les réservoirs de péridotite fracturés.Ces nouvelles données suggèrent un contrôle complexe de la structure des roches ultramafiques dans le processus de serpentinisation et fournissent de nouvelles perspectives pour le stockage potentiel du CO2 dans les réservoirs fracturés à la péridotite. / The hydrothermal alteration of the mantle lithosphere at mid-ocean ridges provides a mechanism for transferring heat and mass between the deep Earth and the overlaying ocean. The mantle lithosphere is constituted by ultramafic rocks, also called Peridotites. They comprise more than 70% of olivine, associated pyroxenes and minor mineral phases. The percolation of seawater into the ultramafic basement produces the alteration of olivine and pyroxenes to serpentine through the so-called serpentinization process and is associated to oxidation and carbonation reactions, the later when CO2 is present. The serpentinization process has special interest on H2 production, CO2 storage, development of life, and the production of economically valuable ore-deposits concentrated at hydrothermal vents. The sustainability and efficiency of the reactions requires penetration and renewal of fluids at the mineral-fluid interface. Oceanic detachment faults and fractures are the highly permeable zones allowing seawater derived fluids to penetrate deeply into the mantle lithosphere. However, the serpentinization process lead to the precipitation of low density minerals that can fill the porous network, clogging flow paths efficiently that may in turn modify the hydrodynamic properties and the reactivity of the reacted rocks.This PhD thesis aims at better understanding the feedback effects of chemical reactions on the hydrodynamic rock properties occurred on highly permeable zones during the earliest stages of alteration of the ultramafic basement. It focuses in particular on the changes in texture and chemical reaction paths of ultramafic rocks by assessing the effects of (i) flow rate and (ii) CO2-rich saline fluids. Two suite of reactive percolation experiments were performed at T=170-190°C and P=25MPa. The first suite of experiments consisted in injecting artificial seawater into porous compressed olivine powder cores over a wide range of constant flow rates. X-Ray µ-tomography of high resolution was acquired before and after the experiment run with high flow rates; in order to evaluate the micro-structural changes of the rock occurred during the serpentinization reaction. The second suite of experiments consisted in injecting CO2-rich saline fluids into peridotite cores mechanically fractured.The results allowed us to differentiate: (1) That, a control of flow infiltration rate at the pore-scale can control the local fluid compositions and the development of different reaction paths at the sample-scale. (2) The development of different reaction paths and textural changes in the rock depends on the concentration of CO2 dissolved in solution. (3) The formation of carbonate minerals (MgCO3) can store CO2 in a form of stable mineral at long-term. (4) A control of the concentration of dissolved CO2(g) and the fracture network can enhance/limit the efficiency of CO2-storage in peridotite fractured reservoirs.These new supporting data suggest a complex control of the structure of the ultramafic rocks in serpentinization process and provides new insights for the potential CO2-storage in peridotite fractured reservoirs.

abstract: Carbon dioxide (CO2) levels in the atmosphere have reached unprecedented levels due to increasing anthropogenic emissions and increasing energy demand. CO2 capture and utilization can aid in stabilizing atmospheric CO2 levels and producing carbon-neutral fuels. Utilizing hollow fiber membranes (HFMs) for microalgal cultivation accomplishes that via bubbleless gas-transfer, preventing CO2 loss to the atmosphere. Various lengths and geometries of HFMs were used to deliver CO2 to a sodium carbonate solution. A model was developed to calculate CO2 flux, mass-transfer coefficient (KL), and volumetric mass-transfer coefficient (KLa) based on carbonate equilibrium and the alkalinity of the solution. The model was also applied to a sparging system, whose performance was compared with that of the HFMs. Typically, HFMs are operated in closed-end mode or open-end mode. The former is characterized by a high transfer efficiency, while the latter provides the advantage of a high transfer rate. HFMs were evaluated for both modes of operation and a varying inlet CO2 concentration to determine the effect of inert gas and water vapor accumulation on transfer rates. For pure CO2, a closed-end module operated as efficiently as an open-end module. Closed-end modules perform significantly worse when CO2-enriched air was supplied. This was shown by the KLa values calculated using the model. Finally, a mass-balance model was constructed for the lumen of the membranes in order to provide insight into the gas-concentration profiles inside the fiber lumen. For dilute CO2 inlet streams, accumulation of inert gases -- nitrogen (N2), oxygen (O2), and water vapor (H2O) -- significantly affected module performance by reducing the average CO2 partial pressure in the membrane and diminishing the amount of interfacial mass-transfer area available for CO2 transfer. / Dissertation/Thesis / Masters Thesis Chemical Engineering 2018